CN114457587A - Anti-fibrillation cellulose fiber and preparation method thereof - Google Patents
Anti-fibrillation cellulose fiber and preparation method thereof Download PDFInfo
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- 230000002378 acidificating effect Effects 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses an antigen fibrillated cellulose fiber and a preparation method thereof. The boric acid or borate without the aldehyde crosslinking agent is added in the cellulose fiber spinning or post-treatment process, and the boric acid or borate is used for crosslinking the cellulose under proper content, proportion and reaction conditions to prepare the cellulose fiber with fibrillation resistance, so that the problem of easy fibrillation of the cellulose fiber is solved, and the processing performance and wearing comfort of the cellulose fiber are improved.
Description
Technical Field
The invention belongs to the technical field of fiber manufacturing, and particularly relates to an anti-fibrillation cellulose fiber and a preparation method thereof.
Background
With the development and progress of science and technology, the gradual exhaustion of traditional energy sources and the increasing awareness of human environmental protection, the development and utilization of green, renewable and environment-friendly novel materials is a necessary trend of polymer development. Because of the non-renewable nature of raw materials based on the traditional petroleum and coal industries, there is an urgent need to develop new materials from renewable resources through green processes to meet the needs of society. Cellulose is one of the most abundant raw materials in nature, and provides properties widely required by people, including biocompatibility, relative stability to most chemical products and the like, so that the development and utilization of cellulose materials in the fields of food, textile, biology, medicine and the like have wide development prospects.
Because the Lyocell product is 100% cellulose, the Lyocell product can be completely biodegraded into inorganic matters of CO2 and H2O in a short time, participates in the substance circulation of an ecological system again, is environment-friendly and pollution-free, and is known as novel green fiber in 21 century. The Lyocell is a regenerated cellulose fiber spun by a dry-wet method by taking pulp as a raw material and N-methylmorpholine-N-oxide (NMMO) as a solvent, compared with viscose fiber, the Lyocell fiber has the advantages of small raw material consumption, simple production process and short flow, the dissolution of the fiber and the NMMO is a pure physical process, the whole production flow is in a water system, no by-product is generated, the recovery rate of the solvent NMMO is up to 99.5%, and the product cellulose can be naturally degraded, has no pollution to the environment and is completely green and environment-friendly.
The Lyocell fibers have the highest level of fibrillation among all regenerated cellulose fibers. After the Lyocell fiber and the fabrics thereof are subjected to the friction action of mechanical external force in a wet state, fine fibrils which are split along the axial direction of the fiber are separated from the surface of the fibrils, so that hairiness is easily generated on the surface of the fiber and the fabrics thereof, and the application of the Lyocell fiber products is severely limited.
At present, the approach to solve the easy fibrillation of Lyocell fibers is mainly to cross-link the fibers or their fabrics. Among them, the patent of invention No. CN103306136A reports that an aldehyde crosslinking agent which is formed by combining oligomeric polybasic acid with molecular weight of 400-1000 and polybasic acid of C2-C6 reacts with cellulose fiber and has obvious effect on the fibrillation resistance of the fiber; in patent report No. CN95192563.6, in order to enhance the crosslinking effect, a crosslinking agent having three acrylamide groups, preferably 1,3, 5-triacrylate hexahydro-1, 3, 5-triazine is used to react with the wet solution-spun cellulose fibers to reduce the fibrillation thereof; however, the cross-linking agents used in the above patents have the problems of aldehyde pollution, complicated synthesis, complex process, etc., respectively, which makes the industrial production of the anti-fibrillation cellulose fibers difficult.
In addition, numerous studies have shown that prolonged contact or wear of formaldehyde-containing fabrics can have a profound effect on human health. There are two main approaches to solve this problem: firstly, the problem of formaldehyde pollution is solved fundamentally, and a novel environment-friendly cross-linking agent capable of replacing urea resin is found. Secondly, the formaldehyde pollution is post-processed, so that the formaldehyde volatilized from the fiber or the fabric can be quickly reduced and stably maintained below a standard value. Therefore, the development of the environment-friendly aldehyde-free crosslinking technology in the process has important research significance on the post-treatment modification of the cellulose fiber.
Disclosure of Invention
In order to further solve the defects of the prior art, the invention aims to provide the antigen fibrillated cellulose fiber and the preparation method thereof, the preparation method is simple, the produced fiber has excellent antigen fibrillation performance, the fiber does not contain aldehyde substances such as formaldehyde, glutaraldehyde and the like, and the requirements of actual processing and application are met.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method of preparing anti-fibrillated cellulose fibres, characterised in that: comprises the following steps of (a) carrying out,
(1) preparing a finish liquor comprising an aldehyde-free crosslinking agent, wherein the aldehyde-free crosslinking agent is boric acid or a borate;
(2) and (3) soaking the cellulose fibers in the finishing liquid, and washing and drying after the soaking to prepare the anti-fibrillation cellulose fibers.
Further, the finishing liquid is prepared by mixing the aldehyde-free cross-linking agent and water in a mass ratio of 1: 1000-1: 100, preferably 1: 600-1: 100, and more preferably 1: 200.
Further, the mass of the aldehyde-free cross-linking agent is 1-60%, preferably 1-40%, and more preferably 20% of the mass of the cellulose fiber.
Further, the cellulose fiber is soaked in the finishing liquid for 2 s-10 min; preferably, 10s-5 min; more preferably, 1 min.
Optionally, the finishing liquid can be placed in a finishing liquid tank and directly applied to a continuous production line of cellulose fibers, and the specific method is as follows: in the production process, the cellulose fiber generated by coagulation in the coagulation bath is immersed in a finishing liquid tank for dipping after being drawn and washed, and the anti-fibrillation cellulose fiber is prepared by washing and drying after the dipping is finished.
Alternatively, commercially available cellulose fibers may be placed in the finishing tank containing the finishing liquor for crosslinking to produce anti-fibrillated cellulose fibers.
The present invention provides another method for producing an anti-fibrillated cellulose fiber, characterized in that: comprises the following steps of (a) carrying out,
(1) adding an aldehyde-free crosslinking agent into the cellulose fiber spinning solution according to the weight ratio to prepare a spinning solution, wherein the aldehyde-free crosslinking agent is boric acid or borate;
(2) and spinning the spinning solution by a wet method or a dry spray wet method, solidifying by a coagulating bath, washing by water, and drying to prepare the anti-fibrillation cellulose fiber.
Further, the weight ratio of the aldehyde-free cross-linking agent to the cellulose fiber spinning solution in the spinning solution is 1:1000 to 50:1000, preferably 2:1000 to 10:1000, and more preferably 3:1000 to 6: 1000.
The invention also provides a preparation method of the anti-fibrillation cellulose fiber, which comprises the following steps:
(1) adding an aldehyde-free cross-linking agent into a cellulose fiber coagulating bath to prepare a coagulating bath solution, wherein the aldehyde-free cross-linking agent is boric acid or borate;
(2) and spinning the cellulose fiber spinning solution by a wet method or a dry spray wet method, solidifying by the coagulating bath solution, washing by water, and drying to prepare the anti-fibrillation cellulose fiber.
Further, the pH values of the finishing liquor and the spinning solution are both 8-11, and the pH value is preferably 10.
Further, when the aldehyde-free crosslinking agent is added to the coagulation bath of cellulose fibers to prepare a coagulation bath solution, and thus to prepare the anti-fibrillated cellulose fibers, the pH of the coagulation bath solution is 8 to 11, preferably 10.
Further, the temperature of the finishing liquid and the temperature of the spinning solution are both 40-70 ℃, preferably 50-60 ℃, and more preferably 60 ℃.
Further, when the aldehyde-free cross-linking agent is added into a cellulose fiber coagulating bath to prepare a coagulating bath solution and further prepare the anti-fibrillation cellulose fibers, the temperature of the coagulating bath solution is 40-70 ℃, preferably 50-60 ℃, and more preferably 60 ℃.
The pH values of the finishing liquid and the spinning solution are adjusted by alkaline substances or alkaline substances and acidic substances, wherein the alkaline substances comprise sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate and the like, the acidic substances comprise hydrochloric acid, nitric acid and the like, preferably sodium carbonate solution, and the concentration of the sodium carbonate solution is 0.0245-0.2043 mol/L, preferably 0.05000-0.1500 mol/L, and more preferably 0.0800-0.1050 mol/L.
Further, when a cross-linking agent boric acid or borate is added to a cellulose fiber coagulation bath to prepare a coagulation bath solution, and further to prepare anti-fibrillated cellulose fibers, the pH of the coagulation bath solution is adjusted by an alkaline substance, or the alkaline substance and an acidic substance, wherein the alkaline substance includes sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate and the like, and the acidic substance includes hydrochloric acid, nitric acid and the like, preferably a sodium carbonate solution, and the concentration of the sodium carbonate solution is 0.0245 to 0.2043mol/L, preferably 0.05000 to 0.1500mol/L, and more preferably 0.0800 to 0.1050 mol/L.
Further, the borate is one or more of metaborate, orthoborate and polyborate, and is preferably sodium tetraborate.
The crosslinking time and the mass ratio of the crosslinking agent can influence the fibrillation resistance effect of the cellulose fiber, when the crosslinking time is short or the mass ratio of the crosslinking agent is low, the crosslinked network structure is easy to deform, the holes are large, the fibrillation resistance of the cellulose fiber is poor, the density of crosslinking points is increased along with the increase of the crosslinking time or the mass ratio of the crosslinking agent, the holes are reduced, the fibrillation resistance of the cellulose fiber is enhanced, and the enhancement effect is obvious, but the deformation resistance of the network structure is poor, the gelation is serious, the mechanical property of the cellulose is reduced, the viscosity of the spinning solution is increased, the processing is difficult, and the practical value is lost. In order to ensure the properties of the anti-fibrillated cellulose fibers, both the crosslinking time and the mass ratio of the crosslinking agent should be controlled within the range defined by the present invention.
Optionally, the cellulose fiber is one or more of Lyocell fiber, viscose fiber, acetate fiber, cuprammonium fiber and other regenerated cellulose fibers.
The invention also provides the antigen fibrillated cellulose fiber obtained by the preparation method.
The invention adds boric acid or borate without aldehyde crosslinking agent into the cellulose fiber post-treatment finishing liquid or spinning solution or coagulating bath. When the crosslinking agent is boric acid, the boric acid is hydrolyzed to form borate, a coordination compound of boron, i.e., boric acid water explains the evolution of borate. When the crosslinking agent is borate, the borate is hydrolyzed in the aqueous solution to generate boric acid, and the boric acid is continuously hydrolyzed to generate the borate which is a coordination compound of boron, namely the borate is hydrolyzed to release the borate. The borate and hydroxyl on the surface of the cellulose react at 40-70 ℃ under an alkaline condition to form a covalent cross-linked network, the chemical reaction formula is shown in figure 1, the hydroxyl on the surface of the cellulose N reacts with the borate P to form cellulose Q containing a covalent cross-linked network structure, no aldehyde cross-linking agent and the cellulose form stable chemical bonds in the covalent cross-linked network, the transverse bonding force among fibrils is enhanced, the possibility of stripping the fibrils from a fiber main body is reduced, and the cellulose fiber with excellent antigen fibrillation performance is obtained.
According to the invention, the cellulose fiber is modified by boric acid or borate without an aldehyde crosslinking agent, the fibrillation resisting effect is obvious, the crosslinking degree of a crosslinking network can be controlled by controlling the content of the crosslinking agent, and the requirements of actual processing and application are met. The method has simple and feasible steps. The used non-aldehyde crosslinking agent is non-toxic, has low cost and no environmental pollution, does not release formaldehyde compounds in the production and storage processes and the process of taking fibers or fabrics treated by the non-aldehyde crosslinking agent, has high durability, and does not absorb chlorine, damage chlorine and yellow.
Drawings
FIG. 1 shows the chemical reaction scheme for reacting borate released by hydrolysis with hydroxyl groups on cellulose fibers.
FIG. 2 is a microscope picture of uncrosslinked Lyocell fibers after ultrasonication treatment for 24 h.
FIG. 3 is a microscope picture of a 1min boric acid crosslinked Lyocell fiber after ultrasonic vibration treatment for 24h in a post-treatment process.
FIG. 4 is a microscope photograph of sodium tetraborate crosslinked Lyocell fiber in the dope after 24h of sonication.
Reference numerals
N: cellulose; p: a borate radical; q cellulose containing a covalently cross-linked network structure
Detailed Description
The invention is further described below with reference to examples.
The fibrillation resistance and mechanical properties of the following anti-fibrillated cellulose fibers were tested using an ultrasonic oscillation treatment method and an electronic single fiber strength meter, respectively.
Example 1
(1) Preparation of finishing liquor:
a finishing liquor was prepared by dissolving 1g of boric acid in 200g of water and heating to 60 ℃ with Na at a concentration of 0.1035mol/L2CO3A solution regulator, which regulates the pH value of the finishing liquid to 10;
(2) preparation of anti-fibrillation Lyocell fiber:
5g of Lyocell fiber is immersed in the finishing liquid for 1 min. And (3) rolling and drying the finishing liquid in the fiber after being taken out, repeatedly washing with water, and then drying in an oven at 60 ℃ to prepare the antigen fibrillated Lyocell fiber.
The mechanical property data are shown in Table 1.
TABLE 1
| Sample (I) | Breaking strength (cN/dtex) | Elongation at Break (%) |
| Uncrosslinked Lyocell fibers | 4.58 | 6.83 |
| Cross-linking 1min Lyocell fibers | 4.39 | 7.47 |
As can be seen from Table 1, the fibrillated Lyocell antigen prepared in example 1 of the present invention has no significant decrease in breaking strength and breaking elongation compared to uncrosslinked Lyocell antigen, indicating that the mechanical properties of fibrillated Lyocell antigen are not impaired by the addition of a crosslinking agent.
FIG. 2 shows a microscope picture of uncrosslinked Lyocell fibers after ultrasonication treatment for 24 h. FIG. 3 shows a microscope picture of boric acid crosslinked 1min Lyocell fibers after 24h ultrasonication.
It can be seen that the uncrosslinked Lyocell fibers have many fibrils stripped from the surface thereof, and the fibers give a hairy appearance, forming pile, i.e., fibrillation. And many fibrils are not stripped from the surface of the Lyocell fiber crosslinked for 1min by boric acid, the surface of the fiber has less plush, and the fibrillation-resistant effect is obvious.
Example 2
(1) Preparation of spinning solution:
300g of sodium tetraborate was added to 60kg of Lyocell fiber dope at room temperature to prepare a spinning solution, and Na was used at a concentration of 0.1035mol/L2CO3A solution regulator, which regulates the pH value of the finishing liquid to 10;
(2) preparation of anti-fibrillation Lyocell fiber:
and (2) mechanically stirring the spinning solution prepared in the step (1) uniformly at the temperature of 60 ℃, defoaming and standing under a vacuum condition, spinning and extruding the spinning solution into a coagulating bath by using a wet method or a dry jet method, washing with water, and drying to prepare the fibrillation-resistant Lyocell fiber. The mechanical property data are shown in Table 2.
TABLE 2
| Sample (I) | Breaking strength (cN/dtex) | Elongation at Break (%) |
| Uncrosslinked Lyocell fibers | 4.58 | 6.83 |
| Crosslinked Lyocell fibers | 4.49 | 7.21 |
As can be seen from Table 2, the sodium tetraborate crosslinked Lyocell fiber prepared in example 2 of the present invention has no significant decrease in breaking strength and breaking elongation compared with uncrosslinked Lyocell fiber, indicating that the mechanical properties of the antigen fibrillated Lyocell fiber are not reduced by the addition of the crosslinking agent.
Fig. 2 shows a microscopic image of uncrosslinked Lyocell fibers after 24h sonication, and fig. 4 shows a microscopic image of antigen fibrillated Lyocell fibers after 24h sonication. It can be seen that the surface of the antigen fibrillated Lyocell fiber prepared in example 2 of the present invention is almost lint-free and the antigen fibrillation effect is significant, compared to uncrosslinked Lyocell fiber.
Claims (8)
1. A method of preparing anti-fibrillated cellulose fibres, characterised in that: comprises the following steps of (a) carrying out,
(1) preparing a finishing liquor containing an aldehyde-free crosslinking agent, wherein the aldehyde-free crosslinking agent is boric acid or borate;
(2) and (3) soaking the cellulose fibers in the finishing liquid, and washing and drying after the soaking to prepare the anti-fibrillation cellulose fibers.
2. The method of producing fibrillation-resistant cellulose fibers of claim 1, further comprising: the finishing liquid is prepared by mixing the aldehyde-free cross-linking agent and water in a mass ratio of 1: 1000-1: 100.
3. The method of producing fibrillation-resistant cellulose fibers of claim 1, further comprising: the mass of the aldehyde-free cross-linking agent is 1-60% of the mass of the cellulose fiber.
4. The method of producing fibrillation-resistant cellulose fibers of claim 1, further comprising: and the cellulose fiber is soaked in the finishing liquid for 2 s-10 min.
5. A method of preparing anti-fibrillated cellulose fibres, characterised in that: comprises the following steps of (a) carrying out,
(1) adding an aldehyde-free crosslinking agent into the cellulose fiber spinning solution according to the weight ratio to prepare a spinning solution, wherein the aldehyde-free crosslinking agent is boric acid or borate;
(2) and spinning the spinning solution by a wet method or a dry spray wet method, solidifying by a coagulating bath, washing by water, and drying to prepare the anti-fibrillation cellulose fiber.
6. The method of producing fibrillation-resistant cellulose fibers of claim 5, further comprising: the weight ratio of the formaldehyde-free cross-linking agent to the cellulose fiber spinning solution in the spinning solution is 1: 1000-50: 1000.
7. Method for the preparation of anti-fibrillated cellulose fibres according to any one of claims 1 and 6, characterized in that: the cellulose fiber is one or more of Lyocell fiber, viscose fiber, acetate fiber and cuprammonium fiber.
8. An anti-fibrillation cellulose fiber characterized by: the anti-fibrillated cellulose fibers are obtained by the production method according to any one of claims 1 and 6.
Priority Applications (1)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT101305B (en) * | 1924-01-23 | 1925-10-26 | Paul Bader | Process for the production of high quality rayon and similar structures from raw viscose. |
| FR690795A (en) * | 1929-03-12 | 1930-09-25 | Soie Artificielle De Tomaszow | Manufacturing process of artificial silk yarns |
| GB398166A (en) * | 1932-02-26 | 1933-08-28 | Henry Dreyfus | Improvements in or relating to the manufacture of artificial filaments, threads, films, fabrics and the like |
| FR1014943A (en) * | 1949-04-05 | 1952-08-25 | American Viscose Corp | Process for the production of artificial fibers from viscose |
| CN102851774A (en) * | 2012-06-06 | 2013-01-02 | 武汉纺织大学 | Method for improving viscose fiber strength |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT101305B (en) * | 1924-01-23 | 1925-10-26 | Paul Bader | Process for the production of high quality rayon and similar structures from raw viscose. |
| FR690795A (en) * | 1929-03-12 | 1930-09-25 | Soie Artificielle De Tomaszow | Manufacturing process of artificial silk yarns |
| GB398166A (en) * | 1932-02-26 | 1933-08-28 | Henry Dreyfus | Improvements in or relating to the manufacture of artificial filaments, threads, films, fabrics and the like |
| US2022411A (en) * | 1932-02-26 | 1935-11-26 | Dreyfus Henry | Manufacture of artificial filaments, threads, films, fabrics, and the like |
| FR1014943A (en) * | 1949-04-05 | 1952-08-25 | American Viscose Corp | Process for the production of artificial fibers from viscose |
| CN102851774A (en) * | 2012-06-06 | 2013-01-02 | 武汉纺织大学 | Method for improving viscose fiber strength |
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